In this paper we discuss the universal selection of exceptional materials for tool making in prehistory. The interpretation suggested in the literature for these non-standard materials is usually limited to a general statement, considering possible aesthetic values or a general, mostly unexplained, symbolic meaning. We discuss the implications of viewing these materials as active agents and living vital beings in Palaeolithic archaeology as attested in indigenous hunter-gatherer communities all around the world. We suggest that the use of specific materials in the Palaeolithic was meaningful, and beyond its possible ‘symbolic’ meaning, it reflects deep familiarity and complex relations of early humans with the world surrounding them—humans and other-than-human persons (animals, plants, water and stones)—on which they were dependent. We discuss the perception of tools and the materials from which they are made as reflecting relationships, respectful behaviour and functionality from an ontological point of view. In this spirit, we suggest re-viewing materials as reflecting social, cosmological and ontological world-views of Palaeolithic humans, and looking beyond their economic, functional aspects, as did, perhaps, our ancestors themselves.